The 22-year-old speedster was named the Reds' Minor League Player of the Year each of the past two seasons after leading two leagues in stolen bases. That includes 2012, when he set a professional baseball record with 155 thefts.
Hamilton, who has been converted from shortstop to center field, led the Triple-A International League with 75 stolen bases this season while hitting .256 with 18 doubles, four triples and six home runs.
St. Louis manager Mike Matheny, a former catcher, knows Molina will be up to the challenge. Going into Monday's game, Molina had thrown out 15 baserunners trying to steal in 35 tries -- 43 percent.
"We have all the confidence in the world that Yadi will throw out anybody he can," Matheny said. "He's doing his part, the pitchers are doing their part."
Some Cardinals pitchers were heard talking about Molina in the St. Louis clubhouse after emerging from a meeting.
"We have film on [Hamilton]," Matheny said. "We're not going to ask the pitchers to be quicker on him or the catchers to throw quicker."
Mark Schmetzer is a contributor to MLB.com. This story was not subject to the approval of Major League Baseball or its clubs.